REACTIONS OF ORGANOALUMINIUM COMPOUNDS WITH ELECTRON DONORS S. P ASYNKIEWICZ Institute of Organic Chemistry and Technology, Technical University ( Politechnika). Warsaw, Poland ABSTRACT The application of organoaluminium compounds as components of organa­ metallic or complex systems is connected with a knowledge of their reactions with electron donors. Reactions with nitriles, ketones, esters, ethers, alkyl chlorides, vinyl chloride, and acid chlorides as the electron donors were investigated. The first stage of the reaction of an organoaluminium compound with an electron donor involves formation of the corresponding donor-acceptor complex. A knowledge of the structure of the formed complexes is very important for an elucidation of the reaction course and mechanism. The heat of formation, composition, and molecular weight of the corresponding complexes were determined, and their i.r. and n.m.r. spectra were studied. From these investigations general conclusions were made concerning, the influence of the Lewis acidity of the organoaluminium compound on the structure of its complexes and on their reactivity; the effect of reactant mole ratio (organoaluminium compound to electron donor) on the reaction course, and thc influence of the molecular structure of the complex and of dislocation of electrons on the reaction mechanism. Hallwachs and Schafarik1 synthesized the first organoaluminium com­ pound 120 years ago. By treating aluminium with ethyl iodide they pre­ pared ethylaluminium sesqui-iodide. However, the chemistry of organo­ aluminium compounds received little attention until the investigations of Ziegler and his collaborators. in about 1950. The development of the direct synthesis of organaalumini um compounds from aluminium. ethylene, and hydrogen, and elaboration of normal pressure polymerization of ethylene, aroused great interest. Almost simul­ taneously, numerous research centres over the world undertook research and technological investigations. Organaaluminium compounds proved to be of both theoretical and technological interest because of their ability to form auto and other complexes, their high reactivity, and associated structure and valence theory problems. In spite of the two decades that have passed since Ziegler's discoveries and the intensive studies that have been conducted throughout. the interest in the chemistry of organoaluminium compounds has not declined. This is mainly due to the use of organoaluminium compounds as constituents of complex catalyst systems. 509 ·S. PASYNKIEWICZ Such systems have been broadly employed in a number of processes including poly-, co-, and oligomerization, alkylation, carbonylation. reduc­ tion, and like processes, Often of prime significance in preparing active catalyst systems is the use of an electron donor which is employed as a solvent or an indispensable activator. Therefore, a knowledge of the reactions of organoaluminium compounds with electron donors may contribute to the elucidation of the nature of catalyst systems and the mechanism of catalysis. The present paper sets out to review the reactions of organoaluminium compounds with organic electron donors. The aluminium atom has free 3p and 3d-orbitals characterized by fairly low energies. They permit ready formation of complexes with electron donors. A first stage of the reaction of an organoaluminium compound with an electron donor involves formation of a complex, which is often stable enough to be separated and finely examined. Thus far complexes of 2 5 organoaluminium compounds with nitriles - , ethers, and esters have been prepared. Complexes with ketones, alkyl chlorides, and acid chlorides have also been postulated. Schematically the formation of a complex may be represented as follows D + AIX 3 ~ D--+ AIX 3 where D = electron donor and X = alkyl, aryl, halogen, etc. At suitable temperatures the complex will enter into further reactions. These may include addition, reduction, elimination, insertion, and cycliza­ tion. lt should be emphasized that with electron donors such as nitriles. ketones. esters. ethers. etc., organoaluminium compounds react in similar fashions and according to like mechanisms. This fact enables some general conclusions to be drawn. the recognition of which may facilitate studies of new reactions. Let us begin by reviewing the reactions of organoaluminium compounds 2 5 with nitriles as electron donors. These reactions atTord 1:1 complexes - which are stable at room temperature, linear in structure, and which may be represented as follows b+ b­ C6H 5--C===N--+ AlR 3 (I) At elevated temperature the complex (I) undergoes an addition reaction to yield an aluminium ketimine derivative 6 7 The addition of trimethylaluminium to benzonitrile - has been investigated extensively. The reaction rate was found to depend on the mole ratio of the reactants. At the ratio of 1 :2 (excess of Me3Al), the addition proceeds at a faster rate than an equimolar reaction. This is explained in terms of the reaction mechanism. 510 REACTIONS OF ORGANOALUMINIUM COMPOUNDS l 2 Owing to a change in hybridization of the nitrogen atom .from sp to sp • the linear complex (I) alters its geometrical structure at elevated tempera­ tures. The R group closely approaches the positively charged carbon atom in the nitrile group, and this may eventually result in R, tagether with an electron pair, being intramolecularly rearranged from the aluminium atom to the carbon atom. With the reactants used in the mole ratio 1 :2, an intermediate complex (II) is formed : C6Hs \+ C==N / \- R ~ AIR 2 \ cl Al--- R I \ R R (II) In this complex, because it is a six-centre system, the R group moves ex­ tremely close to the carbon atom of the nitrile group. lt is this fact that explains why the 1 : 2 addition proceeds faster than the 1 : 1 addition. The above rule relating the rate of addition to the mole ratio of reactants holds true for other electron donors. In addition to the effect of reactant mole ratio on the addition rate, the type of organoaluminium compound is also of consequence. The type of compound highly affects the yield of addition. The mechanism of the reaction remains unaffected, however. The addition yield was studied in relation to the type of methylaluminium compound in its reactions with 8 9 10 benzonitrile , methacrylonitrile , and benzyl cyanide . In these reactions the yield of addition was found to increase in the order, RAIC1 2 < R 2 AICI < R 3Al, that is, to be related to the acid strength of the organoaluminium compound. This dependence is obviously associated with the fact that if the organoaluminium compound is a weak Lewis acid, the R group and its electron pair can be easily abstracted from the aluminium atom. 511 S. PASYNKIEWICZ Cl Cl R ~ ~ I D-AI-R o-AI-R o-Al-R i I I Cl R R Conversely, if the organoaluminium compound is a strong acid (extraction of electrons by the chlorine atoms), abstraction of the R- group is difficult and addition proceeds with low yield. The relevant rule may be formulated as follows: the addition reaction proceeds more readily, the weaker the acidity of the organoaluminium compound. This rule holds true for one type of electron donor. With various donors, the addition reaction proceeds more easily, the stronger the basicity of the donor. The base strength renders abstraction of the R- group from the aluminium atom easier, and thus facilitates addition. In the active complex of an organoaluminium compound with an electron donor, addition proceeds more easily, the larger the positive charge on the nitrile or the carbonyl carbon atom. The following formulae representing the ketone, nitrile, and ester demonstrate that the largest positive charge occurs in the ketone : ....._+ •• - + '+ .. - .. - -C=N: C-0: ' ,c-o: ··/ +'le-g: R-0 R-Q The charge on the nitrile carbon atom is reduced because of partial compen­ sation by the carbon-nitrogen double bond. Similarly, the positive charge on the carbonyl carbon atom in the ester molecule is considerably reduced by a shift of electrons from the OR group towards this carbon atom. Investi­ gations into the effect of positive charge on the yield of addition have been carried out in the reactions of para-substituted esters with triethylalu­ 11 minium . With various substituents X the geometrical structure of. and the steric hindrance in the compound are unaffected and only the electro­ philicity of the carbonyl carbon atom varies ~ ÄIR 3 ~'~-6 ~-I OR Electron-donating substituents reduce the positive charge on the carbon atom and thus render rearrangement difficult. Electron-accepting sub­ stituents have the opposite effect. The yield of reaction is closely dependent on the substituent type and varies fourfold as the substituent is changed from OCH3 to CN. The conclusion tobe drawn isthat the positive charge on the carbon atom to which the R group migrates, is favourable to this rearrangement. Another significant factor operative in addition is the spatial structure of the complex. For the rearrangement to proceed easily the R group must approach the carbon atom. When steric hindrance renders this approach difficult, no addition occurs. This is the case with diisopropyl ketone and 12 triethylaluminium . The two bulky isopropyl groups render the requisite 512 REACTIONS OF ORGANOALUMINIUM COMPOUNDS approach of the ethyl group to the carbonyl carbon atom impracticable, and thus no addition occurs. \o+ H C=O o- / "-.,; /c,' /Al(C2Hs)2 CH3 C C2 H3 Hs The angle between the active carbon atom and the aluminium atom in the resulting complex is also of consequence. If the angle is 180°, as is the case with nitrile complexes, rearrangement is difficult because the R group is a considerable distance from the nitrile group carbon atom. When the angle is less than 180°, L CN-Al = 180° as is the case, e.g. with ketones, rearrangement is feasible. The yield of addition. in relation to the type of substituent at the alumini um atom, has not been thoroughly investigated. However, the existing data 8 indicate that the substituents can be arranged in the following order of decreasing activities: methyl > ethyl > phenyl.